The present invention relates to a process for producing polypropylene from C3 olefins selectively produced from a catalytically cracked or thermally cracked naphtha stream.
The need for low-emissions fuels has created an increased demand for light olefins used use in alkylation, oligomerization, MTBE, and ETBE synthesis processes. In addition, a low cost supply of light olefins, particularly propylene, continues to be in demand to serve as feed for polyolefins production, particularly polypropylene production.
Fixed bed processes for light paraffin dehydrogenation have recently attracted renewed interest for increasing olefins production. However, these types of processes typically require relatively large capital investments as well as high operating costs. It is therefore advantageous to increase olefins yield using processes, which require relatively small capital investment. It would be particularly advantageous to increase olefins yield in catalytic cracking processes.
A problem inherent in producing olefins products using FCC units is that the process depends on a specific catalyst balance to maximize production of light olefins while also achieving high conversion of the 650xc2x0 F.+(xcx9c340xc2x0 C.+) feed components. In addition, even if a specific catalyst balance can be maintained to maximize overall olefins production, olefins selectivity is generally low because of undesirable side reactions, such as extensive cracking, isomerization, aromatization and hydrogen transfer reactions. Light saturated gases produced from undesirable side reactions result in increased costs to recover the desirable light olefins. Therefore, it is desirable to maximize olefins production in a process that allows a high degree of control over the selectivity to C2-C4 olefins that are processed and polymerized to form products such as polypropylene and polyethylene.
An embodiment of the present invention comprises a process for producing polypropylene comprising the steps of (a) contacting a catalyst with a carbonaceous material to pre-coke the catalyst and then (b) contacting a naphtha feed containing between about 10 and about 30 wt. % paraffins and between about 15 and about 70 wt. % olefins with the pre-coked catalyst to form a cracked product, the catalyst comprising about 10 to about 50 wt. % of a crystalline zeolite having an average pore diameter less than about 0.7 nm, the reaction conditions including a temperature from about 500xc2x0 to 650xc2x0 C., a hydrocarbon partial pressure of 10 to 40 psia (70-280 kPa), a hydrocarbon residence time of 1 to 10 seconds, and a catalyst to feed ratio, by weight, of about 4 to 10, wherein no more than about 20 wt. % of paraffins are converted to olefins and wherein propylene comprises at least 90 mol. % of the total C3 products; and, (c) separating the propylene from the cracked product and polymerizing the propylene to form polypropylene.
In another preferred embodiment of the present invention the catalyst is a ZSM-5 type catalyst.
In still another preferred embodiment of the present invention the feed contains about 10 to 30 wt. % paraffins, and from about 20 to 70 wt. % olefins.
In yet another preferred embodiment of the present invention the reaction zone is operated at a temperature from about 525xc2x0 C. to about 600xc2x0 C.
Suitable hydrocarbons feeds for producing the relatively high C2, C3, and C4 olefins yields are those streams boiling in the naphtha range and containing from about 5 wt. % to about 35 wt. %, preferably from about 10 wt. % to about 30 wt. %, and more preferably from about 10 to 25 wt. % paraffins, and from about 15 wt. %, preferably from about 20 wt. % to about 70 wt. % olefins. The feed may also contain naphthenes and aromatics. Naphtha boiling range streams are typically those having a boiling range from about 65xc2x0 F. to about 430xc2x0 F. (18-225xc2x0 C.), preferably from about 65xc2x0 F. to about 300xc2x0 F. (18-150xc2x0 C.).
The naphtha feed can be a thermally-cracked or catalytically-cracked naphtha derived from any appropriate source, including fluid catalytic cracking (FCC) of gas oils and resids or delayed- or fluid-coking of resids. Preferably, the naphtha streams used in the present invention derive from the fluid catalytic cracking of gas oils and resids because the product naphthas are typically rich in olefins and/or diolefins and relatively lean in paraffins.
The process of the present invention is performed in a process unit comprising a reaction zone, a stripping zone, a catalyst regeneration zone, and a fractionation zone. The naphtha feed is fed into the reaction zone where it contacts a source of hot, regenerated catalyst. The hot catalyst vaporizes and cracks the feed at a temperature from about 500xc2x0 C. to 650xc2x0 C., preferably from about 525xc2x0 C. to 600xc2x0 C. The cracking reaction deposits coke on the catalyst, thereby deactivating the catalyst. The cracked products are separated from the coked catalyst and sent to a fractionator. The coked catalyst is passed through the stripping zone where volatiles are stripped from the catalyst particles with steam. The stripping can be preformed under low severity conditions to retain a greater fraction of adsorbed hydrocarbons for heat balance. The stripped catalyst is then passed to the regeneration zone where it is regenerated by burning coke on the catalyst in the presence of an oxygen containing gas, preferably air. Decoking restores catalyst activity and simultaneously heats the catalyst to between about 650xc2x0 C. and about 750xc2x0 C. The hot catalyst is then recycled to the reaction zone to react with fresh naphtha feed. Flue gas formed by burning coke in the regenerator may be treated for removal of particulates and for conversion of carbon monoxide. The cracked products from the reaction zone are sent to a fractionation zone where various products are recovered, particularly a C3 fraction and a C4 fraction.
In another embodiment of the present invention, the catalyst may be pre-coked before contacting the naphtha feed. Pre-coking of the catalyst improves selectivity to propylene. The catalyst can be pre-coked by injecting a coke-producing carbonaceous feed upstream from the point at which the naphtha feed contacts the catalyst. Alternatively, the pre-coking stream can be co-fed with the naphtha feed. Suitable carbonaceous feeds used to pre-coke the catalyst can include, but are not limited to, light cat cycle oil, heavy cat cycle oil, cat slurry bottoms or other heavy, coke producing feeds having a boiling point greater than about 180xc2x0 C., more preferably between about 180xc2x0 C. and about 540xc2x0 C., more preferably between about 200xc2x0 C. and about 480xc2x0 C., and more preferably between about 315xc2x0 C. and about 480xc2x0 C. An added benefit is that delta coke is increased, which provides additional heat in the regenerator needed to heat balance the process.
While attempts have been made to increase light olefins yields in the FCC process unit itself, the practice of the present invention uses its own distinct process unit, as previously described, which receives naphtha from a suitable source in the refinery. The reaction zone is operated at process conditions that will maximize C2 to C4 olefins, particularly propylene, selectivity with relatively high conversion of C5+ olefins. Catalysts suitable for use in the practice of the present invention are those which are comprising a crystalline zeolite having an average pore diameter less than about 0.7 nanometers (nm), said crystalline zeolite comprising from about 10 wt. % to about 50 wt. % of the total fluidized catalyst composition. It is preferred that the crystalline zeolite be selected from the family of medium-pore-size ( less than 0.7 nm) crystalline aluminosilicates, otherwise referred to as zeolites. Of particular interest are the medium-pore zeolites with a silica to alumina molar ratio of less than about 75:1, preferably less than about 50:1, and more preferably less than about 40:1, although some embodiments incorporate silica-to-alumina ratios greater than 40:1. The pore diameter, also referred to as effective pore diameter, is measured using standard adsorption techniques and hydrocarbonaceous compounds of known minimum kinetic diameters. See Breck, Zeolite Molecular Sieves, 1974 and Anderson et al., J. Catalysis 58, 114 (1979), both of which are incorporated herein by reference.
Medium-pore-size zeolites that can be used in the practice of the present invention are described in xe2x80x9cAtlas of Zeolite Structure Types,xe2x80x9d eds. W. H. Meier and D. H. Olson, Butterworth-Heineman, Third Edition, 1992, which is hereby incorporated by reference. The medium-pore-size zeolites generally have a pore size from about 0.5 nm, to about 0.7 nm and include for example, MFI, MFS, MEL, MTW, EUO, MTT, HEU, FER, and TON structure type zeolites (IUPAC Commission of Zeolite Nomenclature). Non-limiting examples of such medium-pore-size zeolites, include ZSM-5, ZSM-12, ZSM-22, ZSM-23, ZSM-34, ZSM-35, ZSM-38, ZSM-48, ZSM-50, silicalite, and silicalite 2. The most preferred is ZSM-5, which is described in U.S. Pat. Nos. 3,702,886 and 3,770,614. ZSM-11 is described in U.S. Pat. No. 3,709,979; ZSM-12 in U.S. Pat. No. 3,832,449; ZSM-21 and ZSM-38 in U.S. Pat. No. 3,948,758; ZSM-23 in U.S. Pat. No. 4,076,842; and ZSM-35 in U.S. Pat. No. 4,016,245. All of the above patents are incorporated herein by reference. Other suitable medium-pore-size zeolites include the silicoaluminophosphates (SAPO), such as SAPO-4 and SAPO-11 which is described in U.S. Pat. No. 4,440,871; chromosilicates; gallium silicates; iron silicates; aluminum phosphates (ALPO), such as ALPO-11 described in U.S. Pat. No. 4,310,440; titanium aluminosilicates (TASO), such as TASO-45 described in EP-A No. 229,295; boron silicates, described in U.S. Pat. No. 4,254,297; titanium aluminophosphates (TAPO), such as TAPO-11 described in U.S. Pat. No. 4,500,651; and iron aluminosilicates.
The medium-pore-size zeolites can include xe2x80x9ccrystalline admixturesxe2x80x9d which are thought to be the result of faults occurring within the crystal or crystalline area during the synthesis of the zeolites. Examples of crystalline admixtures of ZSM-5 and ZSM-11 are disclosed in U.S. Pat. No. 4,229,424, which is incorporated herein by reference. The crystalline admixtures are themselves medium-pore-size zeolites and are not to be confused with physical admixtures of zeolites in which distinct crystals of crystallites of different zeolites are physically present in the same catalyst composite or hydrothermal reaction mixtures.
The catalysts of the present invention are held together with an inorganic oxide matrix material component. The inorganic oxide matrix component binds the catalyst components together so that the catalyst product is hard enough to survive interparticle and reactor wall collisions. The inorganic oxide matrix can be made from an inorganic oxide sol or gel which is dried to xe2x80x9cbindxe2x80x9d the catalyst components together. Preferably, the inorganic oxide matrix is not catalytically active and will be comprising oxides of silicon and aluminum. Preferably, separate alumina phases are incorporated into the inorganic oxide matrix. Species of aluminum oxyhydroxides-xcex3-alumina, boehmite, diaspore, and transitional aluminas such as xcex1-alumina, xcex2-alumina, xcex3-alumina, xcex4-alumina, xcex5-alumina, xcexa-alumina, and xcfx81-alumina can be employed. Preferably, the alumina species is an aluminum trihydroxide such as gibbsite, bayerite, nordstrandite, ordoyelite. The matrix material may also contain phosphorous or aluminum phosphate.
Process conditions include temperatures from about 500xc2x0 C. to about 650xc2x0 C., preferably from about 525xc2x0 C. to 600xc2x0 C., hydrocarbon partial pressures from about 10 to 40 psia (70-280 kPa), preferably from about 20 to 35 psia (140-245 kPa); and a catalyst to naphtha (wt/wt) ratio from about 3 to 12, preferably from about 4 to 10, where catalyst weight is total weight of the catalyst composite. Preferably, steam is concurrently introduced with the naphtha stream into the reaction zone and comprises up to about 50 wt. % of the hydrocarbon feed. Also, it is preferred that the feed residence time in the reaction zone be less than about 10 seconds, for example from about 1 to 10 seconds. These conditions will be such that at least about 60 wt. % of the C5+ olefins in the naphtha stream are converted to C4xe2x88x92 products and less than about 25 wt. %, preferably less than about 20 wt. % of the paraffins are converted to C4xe2x88x92 products, and that propylene comprises at least about 90 mol. %, preferably greater than about 95 mol. % of the total C3 reaction products with the weight ratio of propylene/total C2-products greater than about 3.5.
Preferably, ethylene comprises at least about 90 mol. % of the C2 products, with the weight ratio of propylene:ethylene being greater than about 4, and that the xe2x80x9cfull rangexe2x80x9d C5+ naphtha product is enhanced in both motor and research octanes relative to the naphtha feed. It is also within the scope of this invention to feed an effective amount of single ring aromatics to the reaction zone to also improve the selectivity of propylene versus ethylene. The aromatics may be from an external source such as a reforming process unit or they may consist of heavy naphtha recycle product from the instant process.
The following examples are presented for illustrative purposes only and are not to be taken as limiting the present invention in any way.